EP1555571B1 - Matiere durcie et plaque flexographique comprenant celle-ci - Google Patents

Matiere durcie et plaque flexographique comprenant celle-ci Download PDF

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Publication number
EP1555571B1
EP1555571B1 EP03756700A EP03756700A EP1555571B1 EP 1555571 B1 EP1555571 B1 EP 1555571B1 EP 03756700 A EP03756700 A EP 03756700A EP 03756700 A EP03756700 A EP 03756700A EP 1555571 B1 EP1555571 B1 EP 1555571B1
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EP
European Patent Office
Prior art keywords
curable resin
resin composition
polymer block
block copolymer
cured material
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EP03756700A
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German (de)
English (en)
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EP1555571A1 (fr
EP1555571A4 (fr
Inventor
Kenji c/o Kuraray Co. Ltd. SUZUKI
Kenji c/o Kuraray Co. Ltd. Shachi
Mizuho c/o Kuraray Co. Ltd. Maeda
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/117—Free radical

Definitions

  • the present invention relates to a cured material and a flexographic plate that contains the cured material as its constituent. Containing the cured material as its constituent, the flexographic plate of the present invention is highly strong and extendable in the cured area and can thus be used as flexographic plates that can form a sharp image plate surface even for a fine image.
  • the flexographic plate of the present invention is particularly suitable for printing on cardboard, recycled paper, or other materials having a rough surface.
  • a flexographic plate is a type of relief printing plates and generally includes an elastic relief plate made of rubber or photosensitive resin, to which a liquid ink is applied for printing. Flexographic plates can print on rough or curved surfaces and are thus widely used for printing images on wrapping, magazines, cardboards, labels, and bottles. Flexographic plates were previously manufactured by pouring molten rubber in a mold and then curing the rubber or by manually carving a rubber plate. Neither of these techniques was suitable for producing accurate flexographic plates, however. Lately, the development of a new technique that uses curable resins to make flexographic plate materials has made the production of flexographic plates considerably simple.
  • WO 01/90818 A1 describes a process for preparing flexographic printing plates.
  • US-patent 6,326,127 , US2002/0045129 A1 and WO 00/00546 describe a photo-curable polymer composition and flexographic printing plates containing the same.
  • US-patent 5,496,684 describes photosensitive compositions and elements for flexographic printing.
  • EP-A-0 525 206 describes a photosensitive elastomer composition.
  • EP-A-0 859 284 describes a water-developable photosensitive composition and production process thereof.
  • a typical flexographic plate material of the newly developed type includes, from top to bottom, a surface protective layer; a layer of a curable resin composition that is curable by irradiating with an active energy ray and is composed of an elastomer, such as urethane rubber, butyl rubber, silicon rubber and ethylene propylene rubber, an ethylenic unsaturated compound and, if necessary, a photopolymerization initiator; an adhesive layer; and a substrate (See, for example, " Kankosei jushi no kiso to jitsuyo (Basics and applications of photosensitive resins)" Supervised by Kiyoshi Akamatsu, CMC Co. Ltd. (2001) 152-160 ).
  • a film carrying a negative image of a letter, diagram, picture, pattern, or any other image to be printed is first applied to the surface of the protective film opposite to the substrate.
  • the negative film is then irradiated with an active energy ray from above, so that the predetermined areas of the curable resin composition layer are selectively cured by the action of the active energy ray transmitted through the imaged area of the film and become insoluble to solvent.
  • the negative film and the protective film are removed and a solvent is applied to remove the non-irradiated or uncured areas of the curable resin composition layer (development step) and thereby form an image area (i.e ., image plate surface).
  • thermoplastic elastomer composed of a monovinyl-substituted aromatic hydrocarbon and a conjugated diene is used in conjunction with a diene-based liquid rubber that has a high average proportion of bound vinyl units (See, Japanese Patent Application Laid-Open No. 2000-155418 ).
  • Japanese Patent Publication No. S55-34415 employs crystalline 1,2-polybutadiene in conjunction with a polymer compound, such as polyisoprene rubber, that comprises as its constituents at least one of ethylene, butadiene and isoprene.
  • a drawback of this technique is that the uncrosslinked rubber used in the resin makes the flexographic plate susceptible to deformation (cold flow) during storage or transportation of uncured plates.
  • S51-43374 describes the use of a certain block copolymer (preferably a styrene-isoprene-styrene triblock copolymer or a styrene-butadiene-styrene triblock copolymer having a particular composition) that is a thermoplastic elastomer and in which the hard segments have a glass transition temperature of 25°C or above.
  • a certain block copolymer preferably a styrene-isoprene-styrene triblock copolymer or a styrene-butadiene-styrene triblock copolymer having a particular composition
  • the part of the copolymer formed of polystyrene causes a cohesive force, which reduces deformation of uncured plates.
  • the polystyrene blocks of the elastomer do not undergo crosslinking even when irradiated with an active energy ray, so that the uncrosslinked polystyrene blocks causes a poor solvent resistance of the cured area. Consequently, the image area tends to swell when a solvent is applied to remove the uncured area, resulting in insufficient reproducibility and poor ink resistance of the flexographic plates.
  • Another flaw of this technique is that the strength and extension of the cured area are insufficient especially for forming a fine image area and the resulting flexographic plate becomes less durable. This causes chipping in the edge of the image plate surface during the removal of the uncured area by washing with a solvent and, when necessary, a brush. As a result, the desired sharp image plate surface may not be obtained.
  • the flexibility of flexographic plates is increased by the use of a binder (preferably, a styrene-butadiene-styrene triblock copolymer) containing thermoplastic and elastomeric domains, in combination with a particular addition polymerizable ethylenic unsaturated monomer.
  • a binder preferably, a styrene-butadiene-styrene triblock copolymer
  • the resin according to this technique includes some part formed of a polystyrene block similar to the one described above, which makes the flexographic plate less resistant to solvent.
  • the cured area of the flexographic plate obtained by this technique is not strong enough to form a fine image area.
  • the curable composition underlying the cured material of the present invention can be cured to form strong and extendable areas and can thus be used to make flexographic plates that can form a sharp image plate surface even for a fine image. It is also an objective of the present invention to provide a flexographic plate that uses the cured material as its constituent.
  • the present invention achieves this object by providing the following material:
  • the addition polymerization-based block copolymer (I), the essential component of the curable resin composition underlying the cured material of the present invention, is selected from block copolymers comprising at least one polymer block A and at least one polymer block B, and the hydrogenated products thereof.
  • the polymer block A essentially comprises an aromatic vinyl compound unit that contains at least 10% by mass of an alkylstyrene-derived structural unit (a) in which at least one alkyl group having 1 to 8 carbon atoms is bound to a benzene ring.
  • the polymer block B essentially comprises a conjugated diene compound unit. At least the moiety of polymer block A undergoes crosslinking upon exposure to an ultraviolet ray.
  • alkylstyrenes for forming the structural unit (a) of the polymer block A include o-alkylstyrene, m-alkylstyrene, p-alkylstyrene, 2,4-dialkylstyrene, 3,5-dialkylstyrene, and 2,4,6-trialkylstyrene with their alkyl groups having 1 to 8 carbon atoms, and halogenated alkylstyrenes in which one or more of the hydrogen atoms borne by the alkyl groups of the alkylstyrenes have been substituted with halogen atoms.
  • alkylstyrenes for forming the structural unit (a) include o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 3,5-dimethylstyrene, 2,4,6-trimethylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, 2,4-diethylstyrene, 3,5-diethylstyrene, 2,4,6-triethylstyrene, o-propylstyrene, m-propylstyrene, p-propylstyrene, 2,4-dipropylstyrene, 3,5-dipropylstyrene, 2,4,6-tripropylstyrene, 2-methyl-4-ethylstyrene,
  • the polymer block A may contain one or more units of the above-described alkylstyrenes and halogenated alkylstyrenes for forming the structural unit (a).
  • alkylstyrenes and halogenated alkylstyrenes for forming the structural unit (a).
  • p-methylstyrene unit which can readily undergo crosslinking and is readily available, is particularly preferred as the structural unit (a).
  • the polymer block A contains aromatic vinyl compound units other than those forming the structural unit (a).
  • structural units include those formed of styrene, ⁇ -methylstyrene, ⁇ -methylstyrene, monofluorostyrene, difluorostyrene, monochlorostyrene, dichlorostyrene, methoxystyrene, vinylnaphthalene, vinylanthracene, indene, and acetonaphthylene. Of these, styrene and ⁇ -methylstyrene are particularly preferred.
  • the polymer block A of the addition polymerization-based block copolymer (I) forms hard segments.
  • the proportion of the structural unit (a) in the polymer block A is 10% by mass or more, and preferably 40% by mass or more with respect to the mass of the polymer block A.
  • the polymer block A may be made entirely of the structural unit (a).
  • the structural unit (a) and other aromatic vinyl compound units may be linked to one another either randomly, in blocks or in tapered blocks.
  • the polymer block A is present in the addition polymerization-based block copolymer (I) in an amount of 10 to 40% by mass. If the amount of the polymer block A is less than 10% by mass, then the ability of the polymer block A to physically aggregate to form the hard segments of the addition polymerization-based block copolymer (I) becomes weak. As a result, the uncured plate ( i.e. , flexographic plate material yet to be irradiated with ultraviolet ray) formed of the curable resin composition containing the addition polymerization-based block copolymer (I) becomes susceptible to cold flow. This causes significant deformation of the plate during storage or transportation, making the flexographic plate less suitable for printing. If the amount of the polymer block A is greater than 40% by mass, then the rubber elasticity of the curable resin composition is decreased, making it difficult for the flexographic plate to effectively transfer an ink to cardboards, recycled paper, and other paper articles that have rough surfaces.
  • the polymer block A of the addition polymerization-based block copolymer (I) may include, along with the structural unit composed of the aromatic vinyl compound containing the structural unit (a), a small amount of structural units composed of other polymerizable monomers.
  • the proportion of the structural unit composed of such other polymerizable monomers is preferably 30% by mass or less, and more preferably 10% by mass or less based on the mass of the polymer block A (or the total mass of the polymer blocks A when the addition polymerization-based copolymer (I) contains two or more polymer blocks A).
  • the other polymerizable monomers include 1-butene, pentene, hexene, butadiene, isoprene, and methyl vinyl ether.
  • the addition polymerization-based block copolymer (I) for use in the present invention may contain a polymer block composed of an aromatic vinyl compound that does not contain the structural unit (a).
  • the polymer block B of the addition polymerization-based copolymer (I) is composed essentially of a conjugated diene compound unit.
  • the conjugated diene compounds include butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and 1,3-hexadiene.
  • the polymer block B may be composed solely of one of these conjugated diene compounds, or it may be composed of two or more of the conjugated diene compounds.
  • the polymer block B is preferably composed of butadiene, isoprene, or a mixture of butadiene and isoprene.
  • the type and the amount of the microscopic structure for forming the polymer block B are not limited to a particular type and amount, preferably 5 to 90mol%, more preferably, 20 to 70mol% of the monomer units of the polymer block B are linked by 1,2-linkage when the polymer block B is composed of, for example, butadiene units alone and when the polymer block B is composed of isoprene units alone or combination of butadiene units and isoprene units, 5 to 80mol%, preferably 10 to 60mol% of the monomer units are linked by 1,2-linkage or 3,4-linkage.
  • the monomer units may be linked to one another either randomly, in blocks, in tapered blocks, or by two or more of these manners of linking.
  • the polymer block B may contain, along with the structural units composed of the conjugated diene compounds, a small proportion of structural units composed of other polymerizable monomers.
  • the proportion of such other polymerizable monomers is preferably 30% by mass or less and, more preferably, 10% by mass or less based on the mass of the polymer block B that forms the addition polymerization-based block copolymer (1) (or the total mass of the polymer blocks B when the addition polymerization-based copolymer (I) contains two or more polymer blocks B).
  • the other polymerizable monomers include styrene, ⁇ -methylstyrene, and the aforementioned alkylstyrenes for forming the structural unit (a) (preferably, p-methylstyrene).
  • the polymer block B be one of the followings: a polyisoprene block composed of isoprene units or a hydrogenated polyisoprene block in which some or all of the carbon-carbon double bonds originating from the isoprene units have been hydrogenated; a polybutadiene block composed of butadiene units or a hydrogenated polybutadiene block in which some or all of the carbon-carbon double bonds originating from the butadiene units have been hydrogenated; or a copolymer block composed of isoprene units and butadiene units or a hydrogenated copolymer block in which some or all of the carbon-carbon double bonds originating from the isoprene units or the butadiene units have been hydrogenated.
  • polymer block A and the polymer block B are linked to one another, they may be linked in any manner of linking, forming a straight-chained, branched or radial molecule of the addition polymerization-based block copolymer (I). Two or more of these manners of linking may be combined in one molecule.
  • the polymer block A and the polymer block B are linked together to form a straight-chained molecule.
  • straight-chained molecules examples include triblock copolymers as denoted by A-B-A, tetrablock copolymers as denoted by A-B-A-B and pentablock copolymers as denoted by A-B-A-B-A, given that "A” represents the polymer block A and "B” represents the polymer block B.
  • triblock copolymers (“A-B-A") are particularly preferred because of the flexibility and readiness of the production of the addition polymerization-based block copolymer (I).
  • addition polymerization-based copolymer (I) may have any number average molecular weight, it preferably has a number average molecular weight in the range of 30000 to 1000000, and more preferably in the range of 40000 to 300000.
  • number average molecular weight refers to a number average molecular weight as determined by gel permeation chromatography (GPC) using polystyrene standards.
  • the addition polymerization-based copolymer (I) of the present invention can be produced, for example, by a known anionic polymerization technique. Specifically, the alkylstyrene for forming the structural unit (a), or a mixture of the alkylstyrene for forming the structural unit (a) and the aromatic vinyl compound, and the conjugated diene compound are sequentially polymerized to form a block copolymer ( i.e. , non-hydrogenated form of the addition polymerization-based block copolymer (I)). Using an initiator such as an alkyllithium compound, the reaction is carried out in n-hexane, cyclohexane, or other organic solvents that are inert to the polymerization.
  • an initiator such as an alkyllithium compound
  • the resulting block copolymer is hydrogenated.
  • the hydrogenation reaction is generally carried out in a saturated hydrocarbon solvent such as cyclohexane at a reaction temperature of 20 to 100°C under a hydrogen pressure of 0.1 to 10MPa and in the presence of a hydrogenation catalyst, giving a hydrogenated product of the addition polymerization-based block copolymer (I).
  • hydrogenation catalysts examples include Raney nickels; heterogeneous catalysts containing metals, such as Pt, Pd, Ru, Rh, and Ni, carried by carbon, alumina, diatomite, and other suitable carriers; Ziegler catalysts containing an organic metal compound of, for example, cobalt, nickel and other group 9 or group 10 metals, combined with an organoaluminum compound or organolithium compound, such as triethylaluminum and triisobutylaluminum; and metallocene catalysts containing a bis(cyclopentadienyl) compound of transition metals, such as titanium, zirconium, and hafnium, combined with an organic metal compound, such as lithium, sodium, potassium, aluminum, zinc, and magnesium.
  • heterogeneous catalysts containing metals such as Pt, Pd, Ru, Rh, and Ni, carried by carbon, alumina, diatomite, and other suitable carriers
  • the degree of hydrogenation may be adjusted depending on what physical properties are required of the curable resin composition of the present invention, it is preferred that 70% of more, preferably 85% or more, and more preferably 95% or more of the carbon-carbon double bonds that result from the conjugated diene compound units of the polymer block B for forming the addition polymerization-based block copolymer (I) are hydrogenated when heat resistance, weather resistance, and ozone resistance are particularly important.
  • the degree of hydrogenation of the carbon-carbon double bonds that result from the conjugated diene compound units of the polymer block B can be determined by measuring the amount of the carbon-carbon double bonds in the polymer block B before the hydrogenation reaction and the amount after the hydrogenation reaction by means of iodimetry, IR spectrophotometry, nuclear magnetic resonance or other suitable techniques and taking the difference between these amounts.
  • the addition polymerization-based block copolymer (I) is present in the curable resin composition underlying the cured material of the present invention in an amount of 30 to 99% by mass and, more preferably, in an amount of 50 to 95% by mass. If the amount of the addition polymerization-based block copolymer (I) in the curable resin composition is less than 30% by mass, then the resulting uncured plate (i.e. , flexographic plate material yet to be irradiated with an active energy ray), formed of the curable resin composition, will not be hard enough, so that the plate becomes susceptible to cold flow and, thus, deformation during its storage or transportation. Such flexographic plates are less suitable for printing. If the amount is more than 99% by mass, then the resulting curable resin composition becomes excessively hard, making it difficult for the flexographic plate to effectively transfer an ink to cardboards, recycled paper and other paper articles that have rough surfaces.
  • the amount of the addition polymerization-based block copolymer (I) in the curable resin composition is less
  • the ethylenic unsaturated compound (II) for use in the curable resin composition underlying the cured material of the present invention may be a carboxylic acid having carbon-carbon double bonds, such as acrylic acid, methacrylic acid, fumaric acid, and maleic acid, or an ester thereof (for example, diethyl fumarate, dibutyl fumarate, dioctyl fumarate, distearyl fumarate, butyloctyl fumarate, diphenyl fumarate, dibenzyl fumarate, dibutyl maleate, dioctyl maleate, bis(3-phenylpropyl)fumarate, dilauryl fumarate, and dibehenyl fumarate); (meth)acrylamide, such as acrylamide, methacrylamide, and diacetone acrylamide; an N-substituted maleimide, such as N-n-hexylmaleimide, N-cyclohexylmaleimide, N
  • the ethylenic unsaturated compound (II) is present in the curable resin composition underlying the cured material of the present invention in an amount of 1 to 70% by mass and, more preferably, in an amount of 5 to 50% by mass. If the amount of the ethylenic unsaturated compound (II) present in the curable resin composition is less than 1% by mass, then the resulting uncured plate (i.e ., flexographic plate material yet to be irradiated with ultraviolet ray) made of the curable resin composition may not cure to a sufficient degree upon irradiation with ultraviolet ray. As a result, desired sharp image plate surfaces may not be obtained. If the amount is more than 70% by mass, then the curable resin composition, once cured, becomes excessively hard, making it difficult for the flexographic plate to effectively transfer an ink to cardboards, recycled paper, and other paper articles that have rough surfaces.
  • the amount of the ethylenic unsaturated compound (II) present in the curable resin composition is less than 1%
  • the photopolymerization initiator (III), a mandatory component of the curable resin composition underlying the cured material of the present invention, may be benzophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, ⁇ -methylolbenzoin, ⁇ -methylolbenzoin methyl ether, ⁇ -methoxybenzoin methyl ether, benzoin phenyl ether, and ⁇ -t-butylbenzoin. These compounds may be used either individually or in combination of two or more compounds.
  • the photopolymerization initiator (III) is added to the curable resin composition underlying the cured material of the present invention preferably in an amount of 0.1 to 10% by mass and, more preferably, in an amount of 0.2 to 8% by mass with respect to the total amount of the curable resin composition.
  • the amount of the photopolymerization initiator (III) is less than 0.1% by weight, then the curable resin composition does not undergo crosslinking to a sufficient degree, resulting in that it is hard to obtain sufficient curability.
  • the photopolymerization initiator (III) leads to a reduced transmittance of the curable resin composition to an active energy ray and, thus, a reduced sensitivity to irradiation. As a result, it is hard to form sufficient crosslinking.
  • the softener (IV) is an optional component of the curable resin composition underlying the cured material of the present invention.
  • softeners include diene-based liquid rubbers, such as liquid polyisoprene, liquid 1,2-polybutadiene, liquid 1,4-polybutadiene, liquid poly 1,2-pentadiene, liquid ethylene-butadiene copolymer, liquid acrylonitrile-butadiene copolymer, and modified products and hydrogenated products thereof; petroleum-based softeners, such as paraffin-, naphthene-, and aromatic compound-based processed oils; liquid paraffin; and vegetable oil-based softeners, such as peanut oil and rosin. These softeners may be used either individually or as a mixture of two or more softeners. Of these, diene-based liquid rubber is particularly preferred for use in the present invention.
  • the softener (IV) may be added in any amount that does not affect the objective of the present Invention.
  • the softener is preferably added in an amount of 5 to 50% by mass with respect to the total amount of the curable resin composition.
  • the following polymers may further be added to the curable resin composition underlying the cured material of the present invention: rubbers, such as natural rubbers, synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acryl rubber, butyl rubber, and acrylonitrile-butadiene rubber; and styrene-based block copolymers, such as polystyrene-polyisoprene-polystyrene block copolymers, polystyrene-polybutadiene-polystyrene block copolymers, and hydrogenated products thereof.
  • rubbers such as natural rubbers, synthetic polyisoprene rubber, polybutadiene rubber, styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber, acryl rubber, butyl rubber, and acrylonitrile-butadiene rubber
  • auxiliary additives used in common photosensitive resin compositions may be added to the curable resin composition underlying the cured material.of the present invention, including heat polymerization inhibitors, such as 2,6-di-t-butyl-p-cresol, p-methoxyphenol, pentaerythritol tetrakis[3-(3',5'-di-t-butyl-4'-hydroxy)phenylpropionate], hydroquinone, t-butyl catechol, t-butyl hydroxyanisole, and 4,4'-butylidene bis(3-methyl-6-t-butyl)phenol; UV absorbents; antihalation agents; and photostabilizers. These compounds may be used either individually or in combination of two or more.
  • heat polymerization inhibitors such as 2,6-di-t-butyl-p-cresol, p-methoxyphenol, pentaerythritol tetrakis[3-(3',5'-
  • the curable resin composition underlying the cured material of the present invention can be produced by mixing/kneading the above-described addition polymerization-based block copolymer (I), the ethylenic unsaturated compound (II), and the photopolymerization initiator (III), and, if necessary, the softener (IV), and the other optional additives on, for example, a kneader.
  • the active energy ray that is used to cure the curable resin composition underlying the cured material of the present invention is an ultraviolet wave, may be in combination with a particle beam.
  • the particle beam include electron beam (EB) and ⁇ -ray, and may be accompanied by visible light, infrared ray, ⁇ -ray, and X-ray, either alone or in any combination.
  • EB electron beam
  • These active energy rays can be irradiated using known apparatuses.
  • the electron beam may be accelerated at a voltage of 0.1 to 10MeV and irradiated at a dose of 1 to 500kGy.
  • a lamp with an irradiation wavelength of 200 to 450 nm may be preferably used as the source of ultraviolet ray (UV).
  • Examples of the electron beam (EB) source include tungsten filament, and examples of the ultraviolet ray (UV) source include low-pressure mercury-vapor lamp, high-pressure mercury-vapor lamp, ultraviolet mercury lamp, carbon arc lamp, xenon lamp, and zirconium lamp.
  • EB electron beam
  • UV ultraviolet ray
  • the curable resin composition underlying the cured material of the present invention is particularly suitable for use as a constituent of flexographic plates.
  • the use of the curable resin composition underlying the cured material of the present invention as a constituent can allow production of flexographic plates that undergo minimum deformation (cold flow) during storage or transportation of uncured plates ( i . e ., flexographic plate material yet to be irradiated with ultraviolet ray), are ideal for printing sharp images, and that can ensure high quality printing in printing on cardboards, recycled paper, and other poor quality paper articles having rough surfaces by being capable of effectively transferring an ink onto such paper articles.
  • a preferred technique for producing a flexographic plate material that uses the curable resin composition underlying the cured material of the present invention as a constituent involves molding the molten curable resin composition underlying the cured material of the present invention into a desired shape by using press molding, extrusion molding, or calendering.
  • the composition is molded such that it is deposited on a substrate to a thickness of approximately 200 ⁇ m to 20mm.
  • the substrate may be a plastic sheet, rubber sheet, foamed olefin sheet, foamed rubber sheet, foamed urethane sheet, or metal sheet. If necessary, an adhesive may be used to adhere the substrate to the curable resin composition underlying the cured material of the present invention.
  • a protective film such as a polyethylene terephthalate film, may be applied to the surface of the curable resin composition so as to keep the curable resin composition underlying the cured material of the present invention from being affected by oxygen present in the atmosphere.
  • One exemplary technique for obtaining a flexographic plate from the flexographic plate material using the curable resin composition underlying the cured material of the present invention as a constituent includes the following procedures: First, the surface protective film, if any, is removed. A film carrying a negative image of a Letter, diagram, picture, pattern or any other image to be printed is then applied to the layer of the curable resin composition of the present invention. The negative film is irradiated with ultraviolet ray from above, so that the predetermined area of the curable resin composition layer is selectively cured by the action of the active energy ray transmitted through the imaged area of the negative film and become insoluble to solvent. Subsequently, the negative film is removed and a solvent is applied to remove the non-irradiated or uncured area of the curable resin composition layer and thereby form an image area.
  • solvents that can be used to remove the uncured area include tetrachloroethylene, aromatic hydrocarbons, such as, toluene and xylene, acetates, limonene, and decahydronaphthalene, as well as mixtures of these solvents with n-butanol, 1-pentanol, and benzyl alcohol.
  • the unexposed area i.e ., uncured area of the curable resin composition
  • may be dissolved away for example, by applying the solvent sprayed from a nozzle or by washing with the solvent and a brush.
  • the flexographic plate material obtained by using the curable resin composition underlying the cured material of the present invention as a constituent undergoes minimum deformation during storage or transportation of uncured plates (i.e. , flexographic plate material yet to be irradiated with ultraviolet ray).
  • the flexographic plate of the present invention can form a sharp image plate surface by irradiating the flexographic plate material with ultraviolet ray, and can ensure high quality printing in printing on cardboards, recycled paper, and other poor quality paper articles with rough surfaces by being capable of effectively transferring an ink onto such paper articles.
  • the present invention thus provides a cured material from a curable resin composition suitable for the production of a flexographic plate that allows printing on an article with rough surfaces, such as cardboard and recycled paper.
  • the curable composition underlying the cured material of the present invention can be cured to form strong and extendable areas and can thus be used to make flexographic plates that can form a sharp image plate surface even for a fine image.
  • the present invention also provides a flexographic plate that uses the cured material as its constituent, wherein the flexographic plate material uses the curable resin composition underlying the cured material of the present invention as its constituent, wherein the flexographic plate material is irradiated.
  • a 2mm-thick sheet made of each of the curable resin compositions obtained in Examples and Comparative Examples was cut into a 5cm long ⁇ 5cm wide sample piece. While a 30g/cm 2 load was applied to the entire surface of the sample piece, the sample piece was left in a 40°C atmosphere for 24 hours. Subsequently, the thickness of the sample piece was measured and the sample was determined to be "acceptable” if the decrease in thickness was less than 2% (indicated by a circle) and "not acceptable” if the decrease in thickness was 2% or more (indicated by a cross).
  • a No. 5 dumbbell-shaped sample piece as specified by JIS K 6251 was made out of the sheet and was stretched on an INSTRON universal tester at a rate of 500mm/min at 23°C to determine the tensile strength at break (MPa) and the elongation at break (%).
  • a 15cm x 15cm sample piece was cut out from a 2mm-thick pressed sheet made of each of the curable resin compositions obtained in Examples and Comparative Examples.
  • the negative film was then removed and the uncured area (unexposed area) was dissolved by toluene and was scraped off with the help of a brush.
  • the resulting plate was observed for how well the thin lines forming projected areas are reproduced and recessed areas are carved.
  • the sample was determined to be "acceptable” if the negative image was precisely reproduced without cracking or chipping of the image (indicated by "G”) and "non-acceptable” if the reproduction was insufficient (indicated by "NG”).
  • block copolymer (I)-1 a poly(p-methylstyrene)-polybutadiene-poly(p-methylstyrene) triblock copolymer (which is referred to as "block copolymer (I)-1," hereinafter).
  • the resulting block copolymer (I)-1 had a number average molecular weight of 76400, and the amount of p-methylstyrene as determined by 1 H-NMR was 30% by mass. It was determined that 40mol% of the butadiene units forming the polybutadiene block were linked by 1,2-linkage.
  • a hydrogenation catalyst separately prepared by adding 400g of triisopropylaluminum (20% by mass, cyclohexane solution) to 130g of nickel octanoate (64% by mass, cyclohexane solution), was added, and the hydrogenation reaction was allowed to proceed at 80°C in a hydrogen atmosphere of 1MPa.
  • This gave a hydrogenated product of the poly p-methylstyrene-polybutadiene-poly p-methylstyrene triblock copolymer (The product is referred to as "block copolymer (I)-2," hereinafter).
  • the resulting block copolymer (I)-2 had a number average molecular weight of 77000, and the amount of p-methylstyrene and the degree of hydrogenation as determined by 1 H-NMR were 29% by mass and 97%, respectively.
  • block copolymer (I)-3 a poly(p-methylstyrene)-polyisoprene-poly(p-methylstyrene) triblock copolymer (which is referred to as "block copolymer (I)-3," hereinafter).
  • the resulting block copolymer (I)-3 had a number average molecular weight of 127000, and the amount of p-methylstyrene as determined by 1 H-NMR was 20% by mass. It was determined that 40mol% of the isoprene units forming the isoprene block were linked by 1,2-linkage or 3,4-linkage.
  • block copolymer 1 a polystyrene-polybutadiene-polystyrene triblock copolymer (which is referred to as "block copolymer 1" hereinafter).
  • the resulting block copolymer 1 had a number average molecular weight of 76400, and the amount of styrene as determined by 1 H-NMR was 30% by mass. It was determined that 40mol% of the butadiene units forming the polybutadiene block were linked by 1,2-linkage.
  • a hydrogenation catalyst separately prepared by adding 400g of triisopropylaluminum (20% by mass, cyclohexane solution) to 130g of nickel octanoate (64% by mass, cyclohexane solution), was added, and the hydrogenation reaction was allowed to proceed at 80°C in a hydrogen atmosphere of 1MPa.
  • the resulting block copolymer 2 had a number average molecular weight of 77000, and the amount of styrene and the degree of hydrogenation as determined by 1 H-NMR were 29% by mass and 97%, respectively.
  • block copolymer 3 a polystyrene-polyisoprene-polystyrene triblock copolymer (which is referred to as "block copolymer 3" hereinafter).
  • the resulting block copolymer 3 had a number average molecular weight of 127000, and the amount of styrene as determined by 1 H-NMR was 20% by mass. It was determined that 40mol% of the isoprene units forming the polyisoprene block were linked by 1,2-linkage or 3,4-linkage.
  • Block copolymer (I)-2 86 Block copolymer (I)-3 86 71 Block copolymer 2 86 Block copolymer 3 86 71 1,9-nonanediol diacrylate 10 10 25 10 10 25 Benzophenone 3 3 3 3 3 2,6-di-t-butyl cresol 1 1 1 1 1 1 1 tensile strength at break (MPa) 10 12 8.6 6.8 7.2 5.8 elongation at break (%) 440 480 320 220 260 210 Shape stability of uncured plate G G G G NG NG Reproducibility of negative image G G G NG G G G
  • a comparison between Examples 1 through 3 and respective Comparative Examples 1 through 3 indicates that each of the sheets obtained by irradiating respective sheets of the curable resin compositions underlying the cured material of the present invention shows a superior tensile strength at break and an improved elongation at break. This suggests that when used as a material of a flexographic plate, these compositions are each expected to improve the tensile strength at break and elongation at break of the cured area of the plate.
  • the sheets made of the curable resin compositions of Examples 1 through 3 exhibit a better shape stability of uncured plate as compared to those of respective Comparative Examples 1 through 3.
  • each of the sheets made of the curable resin compositions underlying the cured material of the present invention is expected to offer an improved reproducibility of negative images when actually used in the production of flexographic plates ( i.e. , application of negative film, followed by irradiation with a UV ray, followed by removal of uncured area).
  • Block copolymer (I)-1 60 Block copolymer (I)-2 60 Block copolymer (I)-3 60 Block copolymer 1 60 Block copolymer 2 60 Block copolymer 3 60 Liquid polybutadiene (NISSO-PB C-1000) 33 33 33 33 33 33 33 1,9-nonanediol diacrylate 5 5 5 5 5 5 5 Benzophenone 1.5 1.5 1.5 1.5 1.5 2,6-di-t-butyl cresol 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 tensile strength at break (MPa) 8.1 7.0 7.2 4.8 4.2 4.3 elongation at break (%) 300 380 420 200 210 220 Shape stability of uncured plate G G G NG G NG Reproducibility of negative image G G G NG NG G
  • a comparison between Examples 4 through 6 and respective Comparative Examples 4 through 6 indicates that each of the sheets obtained by irradiating respective sheets of the curable resin compositions underlying the cured material of the present invention shows a superior tensile strength at break and an improved elongation at break. This suggests that when used as a material of a flexographic plate, these compositions are each expected to improve the tensile strength at break and elongation at break of the cured area of the plate.
  • the sheets made of the curable resin compositions of Examples 4 through 6 exhibit a better shape stability of uncured plate as compared to those of respective Comparative Examples 4 through 6.
  • each of the sheets made of the curable resin compositions underlying the cured material of the present invention is expected to offer an improved reproducibility of negative images when actually used in the production of flexographic plates ( i.e ., application of negative film, followed by irradiation with a UV ray, followed by removal of uncured area).
  • the flexographic plate material using the curable resin composition underlying the cured material of the present invention as its constituent can be cured to form strong and extendable areas and can be used to make flexographic plates that can form a sharp image plate surface even for a fine image.
  • the flexographic plate of the present invention is particularly useful in printing on cardboards, recycled paper or other paper articles with rough surfaces.
  • the present invention allows production of flexographic plates that undergo minimum deformation during storage or transportation of uncured plates (i.e ., flexographic plate material yet to be irradiated with ultraviolet ray), can form a sharp image plate surface by irradiating with the active energy ray, and can ensure high quality printing in printing on cardboards, recycled paper and other poor quality paper articles having rough surfaces by being capable of effectively transferring an ink onto such paper articles.
  • uncured plates i.e ., flexographic plate material yet to be irradiated with ultraviolet ray

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  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Materials For Photolithography (AREA)
  • Polymerisation Methods In General (AREA)
  • Laminated Bodies (AREA)
  • Printing Plates And Materials Therefor (AREA)
  • Printing Methods (AREA)

Claims (4)

  1. Matériau durci, pouvant être obtenu en irradiant une composition de résine durcissable avec un rayonnement ultraviolet de manière à réticuler un groupe fonctionnel d'une séquence polymère A contenu dans la composition de résine durcissable, la composition de résine durcissable contenant un copolymère séquencé (I) basé sur une polymérisation par addition, un composé éthylénique insaturé (II) et un initiateur de photopolymérisation (III), dans lequel :
    le copolymère séquencé (I) basé sur une polymérisation par addition est choisi parmi des copolymères séquencés comprenant au moins une séquence polymère A et au moins une séquence polymère B, et les produits hydrogénés de ceux-ci ;
    la séquence polymère A comprend essentiellement un motif de composé aromatique vinylique contenant au moins 10 % en poids d'un motif structurel (a) dérivé d'un alkylstyrène dans lequel au moins un groupe alkyle contenant 1 à 8 atomes de carbone est lié à un cycle benzénique ; et la séquence polymère B comprend essentiellement un motif de composé diénique conjugué.
  2. Matériau durci selon la revendication 1, dans lequel la composition de résine durcissable contient en outre un plastifiant (IV).
  3. Matériau durci selon la revendication 1 ou 2, dans lequel le motif structurel (a) dans lequel au moins un groupe alkyle contenant 1 à 8 atomes de carbone est lié à un cycle benzénique est un motif p-méthylstyrène.
  4. Plaque flexographique contenant le matériau durci selon l'une quelconque des revendications 1 à 3.
EP03756700A 2002-10-23 2003-10-20 Matiere durcie et plaque flexographique comprenant celle-ci Expired - Lifetime EP1555571B1 (fr)

Applications Claiming Priority (3)

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JP2002308620 2002-10-23
JP2002308620 2002-10-23
PCT/JP2003/013377 WO2004038503A1 (fr) 2002-10-23 2003-10-20 Composition de resine durcissable et matiere constitutive de plaques flexographiques comprenant la composition de resine durcissable

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CN (1) CN1732407B (fr)
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AU (1) AU2003301625A1 (fr)
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DE60302225T2 (de) * 2003-06-13 2006-08-10 3M Espe Ag Gleichmässig gefärbte Gerüstkeramik sowie Färbelösung
JP4651037B2 (ja) * 2004-06-11 2011-03-16 旭化成イーマテリアルズ株式会社 フレキソ印刷版用感光性樹脂
JP4482032B2 (ja) * 2005-05-11 2010-06-16 旭化成イーマテリアルズ株式会社 感光性樹脂組成物
JP4748812B2 (ja) * 2005-11-21 2011-08-17 旭化成イーマテリアルズ株式会社 フレキソ印刷版
JP5531226B2 (ja) * 2006-10-20 2014-06-25 国立大学法人 名古屋工業大学 ミクロ相分離構造体、固定化されたミクロ相分離構造体、および該構造体を備えた波長可変レーザー発振器、温度センサー、及び光フィルター
EP1961719A1 (fr) * 2007-02-08 2008-08-27 3M Innovative Properties Company Solution de coloration pour structure céramique dentaire et procédés associés
EP2025659A1 (fr) * 2007-07-23 2009-02-18 3M Innovative Properties Company Solution de coloration pour articles dentaires en céramique et procédés associés
US7704676B2 (en) * 2007-09-04 2010-04-27 Kraton Polymers U.S. Llc Block copolymers having distinct isoprene and butadiene midblocks, method for making same, and uses for such block copolymers
US20110064883A1 (en) 2009-09-16 2011-03-17 Nike, Inc. Method Of Post-Mold Crosslinking Thermoplastic Polyurethane Golf Ball Cover Compositions
US8703860B2 (en) 2012-09-19 2014-04-22 Kraton Polymers U.S. Llc Paramethylstyrene block copolymers and their use
CN105007883B (zh) 2013-03-12 2018-03-27 3M创新有限公司 赋予牙科陶瓷荧光的着色溶液
US20220411637A1 (en) 2017-01-26 2022-12-29 Dynasol Elastómeros, S.A. De C.V. Counter Tapered Thermoplastic Elastomers

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EP1555571A1 (fr) 2005-07-20
CN1732407A (zh) 2006-02-08
CN1732407B (zh) 2010-07-21
AU2003301625A1 (en) 2004-05-13
KR20050074489A (ko) 2005-07-18
CA2502204C (fr) 2012-07-31
EP1555571A4 (fr) 2006-06-07
ATE421113T1 (de) 2009-01-15
US7432037B2 (en) 2008-10-07
CA2502204A1 (fr) 2004-05-06
WO2004038503A1 (fr) 2004-05-06
US20060167168A1 (en) 2006-07-27
DE60325877D1 (de) 2009-03-05

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